Diagnostic methods and apparatus for electrodialysis
The present disclosure is directed to ion-exchange systems and devices that can monitor key parameters related to the performance of the ion-exchange device. Specifically, the ion-exchange systems and devices disclosed herein can provide real time voltage drop across groups of membrane pairs using diagnostic spacer borders between the pairs. In addition, the ion-exchange systems and devices disclosed herein can monitor the compression force applied by the compression plates holding the ion-exchange systems and devices together.
This application is a divisional application of U.S. patent application Ser. No. 16/600,416, filed Oct. 11, 2019, which claims the benefit of U.S. Provisional Application No. 62/745,010, filed Oct. 12, 2018, the entire contents of each of which are incorporated herein by reference.
FIELD OF THE DISCLOSUREThis disclosure relates to ion-exchange devices that can monitor key parameters related to the performance of the device during use. More specifically, this disclosure relates to ion-exchange devices capable of measuring voltage drop across groups of membrane pairs and monitoring the compression force applied by the compression plates holding the assembly together.
BACKGROUND OF THE INVENTIONThe earliest forms of large scale desalination were thermal methods such as thermal distillation where the water is boiled and converted into steam, leaving behind the impurities, and the clean steam is collected and condensed. Unfortunately, this is a very energy intensive operation due to the requirement that the water undergo a phase change to separate the unwanted constituents. The energy required for this transformation is far greater than what would be required to separate the constituents if the water remained in the liquid phase.
In order to reduce the energy consumption, membrane based methods were created such as electro-chemical based electrodialysis and pressure driven reverse osmosis. In both of these methods, the water is purified through a membrane which allows the system to create potable water with reduced energy consumption. Electrodialysis can be used to selectively remove positive and negative ions from a water source (e.g., brackish water or the brine solution produced in reverse osmosis units) through transportation of salt ions from one solution to another via ion-exchange membranes upon application of an electrical current. An electrodialysis device can include a pair of electrodes (where a voltage is applied to initiate an electrochemical reaction), alternating anionic and cationic exchange membranes (which can selectively separate ions from one stream while concentrating said ions in adjacent streams from a dilute solution feed stream to a concentrate stream), and spacer materials. This electrochemical desalination method can provide an energy efficient desalination process. To increase the process capacity, pairs of ion exchange membranes can be stacked on top of each other to form stacks which can range from 1 pair to over 1000 pairs of ion exchange membranes.
Unfortunately, the nature of the stacks makes it inherently difficult to identify issues from the assembly process. The performance of a membrane stack can be tested by applying a voltage after assembly. However, if a cell fails to meet the expected metrics, there is currently no easy method of identifying the location of the assembly error much less if it was caused by improper membrane pair lay-up or unidentified damage to the components making up the membrane assembly. Existing attempts to obtain this information include wetting the side of the membrane assembly and forcing the tip of a volt meter into the side of the assembly. However, any readings from this method are inconsistent and endanger operators by placing them in contact with high direct current voltage (sometimes more than 600V). Furthermore, some assemblies may be sealed in such a way that makes the above described method unreliable or impossible to conduct.
As mentioned above, it is difficult to identify the root cause of various operational issues. These operational issues can include the formation of blockages for flow paths in a layer possible due to scale formation or ingress of solids into the system. Current methods for identifying such issues include the one stated above and monitoring hydraulic data to identify increased flow resistance. However, in order to see variations in hydraulic data can require a significant amount of blockage to form which can take a long time since scale formation is often very gradual.
Another common issue in electrochemical membrane assemblies can be the formation of internal leaks between cell pairs. Sealing between pairs of membranes is often accomplished using large plates typically compressed using blots or tie rods. Leakages typically form due to the gradual loosening of bolts over time or through variations in the thickness of the components of the membrane assembly itself. The membranes often include hydrophilic functional groups that attract water. This attraction can result in a swelling of the membranes. The degree of swelling can be directly related to the constituents in the fluid in contact with the membrane. Thus, under changing conditions the stack assembly, which often includes hundreds of membrane pairs, may change in size over time. The change in size may lead to insufficient compression from the compression plates which can cause the formation of internal leaks
BRIEF SUMMARY OF THE INVENTIONApplicants have discovered methods and apparatuses for monitoring key parameters relating to the performance of a membrane assembly during electrochemical ion separation such as desalination. Specifically, Applicants have discovered methods and apparatus for in situ monitoring of the voltage drop across groups of membrane pairs that compose the larger membrane assembly and monitoring the compression force applied by the compression plates holding the membrane assembly together.
In some embodiments, a diagnostic spacer border for an ion exchange device includes a groove in a surface of the spacer border; an electrode, wherein at least a portion of the electrode is in the groove; and a wire lead connected to the electrode. In some embodiments, the diagnostic spacer border includes an internal cavity, wherein a portion of the electrode protrudes from the groove into the internal cavity. In some embodiments, the wire lead and the electrode are connected by a solder joint. In some embodiments, the groove comprises a cured polymer solution. In some embodiments, the diagnostic spacer border includes a tab protruding from a perimeter of the spacer border away from the internal cavity. In some embodiments, the wire lead is connected to the electrode on the tab. In some embodiments, the tab is coated with a graphitic mixture. In some embodiments, the electrode is a wire electrode. In some embodiments, the wire electrode comprises titanium, platinum, or gold. In some embodiments, the electrode is a graphite electrode. In some embodiments, the electrode comprises a graphite electrode and a wire electrode.
In some embodiments, a method of making a diagnostic spacer border for an ion exchange device, the method includes etching a groove into a surface of a spacer border having an internal cavity; inserting a first portion of an electrode into the groove of the spacer border such that a second portion of the electrode protrudes from the groove into the internal cavity; applying a curable polymer solution to the groove; curing the curable polymer solution; and connecting a wire lead to the first portion of the electrode. In some embodiments, the wire lead is connected to the first portion of the electrode by soldering a solder joint between the wire lead and the first portion of the electrode. In some embodiments, the etching is laser etching or chemical etching. In some embodiments, the electrode is a wire electrode. In some embodiments, the wire electrode comprises titanium, platinum, or gold. In some embodiments, the electrode is a graphite electrode. In some embodiments, the electrode comprises a graphite electrode and a wire electrode.
In some embodiments, an ion-exchange device includes a pair of electrodes comprising an anode and a cathode; a first ion exchange membrane and a second ion exchange membrane between the pair of electrodes, a diagnostic spacer border between the first ion exchange membrane and the second ion exchange membrane, the diagnostic spacer border comprising: a groove in a surface of the spacer border; an embedded electrode, wherein at least a portion of the embedded electrode is in the groove; and a wire lead connected to the embedded electrode. In some embodiments, the first ion exchange membrane is a cation exchange membrane and the second ion exchange membrane is an anion exchange membrane.
In some embodiments, an ion-exchange device includes a pair of compression plates, wherein at least one of the compression plates comprises a strain gauge on an outer surface of the at least one compression plate; a pair of electrodes comprising an anode and a cathode between the pair of compression plates; a first ion exchange membrane and a second ion exchange membrane between the pair of electrodes, wherein the first ion exchange membrane comprise at least two inlet or outlet ports, wherein the strain gauge is located at a position on the outer surface of the at least one compression plate corresponding to a point between the at least two inlet or outlet ports of the first ion exchange membrane. In some embodiments, the first ion exchange membrane is a cation exchange membrane and the second ion exchange membrane is an anion exchange membrane. In some embodiments, the position of the strain gauge on the outer surface of the at least one compression plate is equidistant between the at least two inlet or outlet ports of the first ion exchange membrane. In some embodiments, the strain gauge is connected to a data acquisition device. In some embodiments, the strain gauge is attached to the outer surface of at least one compression plate via adhesive.
Additional advantages will be readily apparent to those skilled in the art from the following detailed description. The examples and descriptions herein are to be regarded as illustrative in nature and not restrictive.
All publications, including patent documents, scientific articles and databases, referred to in this application are incorporated by reference in their entirety for all purposes to the same extent as if each individual publication were individually incorporated by reference. If a definition set forth herein is contrary to or otherwise inconsistent with a definition set forth in the patents, applications, published applications and other publications that are herein incorporated by reference, the definition set forth herein prevails over the definition that is incorporated herein by reference.
Exemplary embodiments are described with reference to the accompanying figures, in which:
Unless stated otherwise, like reference numbers in the Figures refer to the same component.
DETAILED DESCRIPTION OF THE INVENTIONVoltage drops across membrane pairs and the membrane assembly can be an indication of the internal health of the system. Operational parameters that can result in variations in pressure drop include, but are not limited to, blockages, internal leaks, and scale formation. Applicants have discovered a way to actively monitor the voltage drop across various membrane groups using a system of embedded diagnostic electrodes.
The ion-exchange systems and devices disclosed herein can include at least one pair of electrodes and at least one pair of ion exchange membranes placed there between. The at least one pair of ion exchange membranes can include a cation exchange membrane and an anion exchange membrane. In some embodiments, at least one of the cation exchange membrane and anion exchange membranes has spacers on the surface facing the other exchange membrane in the ion exchange system/device, as disclosed in U.S. Provisional Application No. 62/689,357, which is hereby incorporated by reference in its entirety.
The electrolyte fluid channels and streams can be in direct contact with the electrodes. In addition, these electrolyte streams may include the same or different fluid as the fluid entering the influent. For example, the electrolyte streams can be a variety of conductive fluids including, but not limited to, raw influent, a separately managed electrolyte fluid, NaCl solution, sodium sulfate solution, or iron chloride solution.
In an ion exchange system such as the one shown in
The influent stream can be converted into a brine stream which is typically waste and a product/diluate stream. The product stream can have a lower ionic concentration. In some embodiments, the product stream can have a predetermined treatment level. For example, the ion exchange system can remove many types of ions or it could focus or be selective to a specific ion type. Examples of groups of ions can include, but are not limited to, monovalent and divalent. Examples of specific ions can include, but are not limited to, arsenic, fluoride, perchlorate, lithium, gold, and silver. They ion exchange system can be held together using a compression system represented in
To create the fluid channels between the membranes, spacer borders can be inserted between the membranes.
When these components are sandwiched together, the holes in the corners of the various components shown in
Each membrane can include four holes which when combined with the spacer borders create a manifold along the length of the electrochemical cell. The manifold holes and the geometry of the spacers can allow fluids to flow into and through the contained area created by the spacer border. In
The first spacer border (from left to right) in
The diagnostic spacer border can include at least one embedded electrode 3. The embedded electrode can provide a voltage lead between the internal chamber 4 and outside 5 of the spacer border. In addition, the embedded electrode can extend into the internal cavity of the spacer border such that it has a large area of electrical contact with any fluid that flows through the internal cavity of the spacer border. The portion of the electrode disposed to the internal cavity of the spacer border can directly contact fluids being treated by the membrane assembly. The diagnostic spacer border can also include a solder joint 6 that creates an electrical junction between the embedded electrode and a wire lead 7. The wire lead can then be connected to a volt meter. The tab can provide additional strain relief and support to the embedded electrode and a place to fasten the volt meter lead.
The embedded electrode can be affixed in a groove 8 cut in the spacer border using a curable polymer solution 9.
In step 502, the diagnostic spacer border has a groove etched into a surface of the spacer border that allows an electrode to be embedded within. The groove can be etched with laser etching, chemical etching, abrading, or cutting into the surface of the spacer border to allow an electrode to be embedded within the groove. In some embodiments, the groove 8 extends only partially through the surface of a spacer border as shown in
In some embodiments, the embedded electrode is an inert electrode. In some embodiments, the embedded electrode can be an inert metal wire such as titanium, platinum, or gold between 0.001″ and 0.020″ thick. In some embodiments, the embedded electrode can be graphite or graphite composite. Such a graphite electrode can be applied to a groove in the spacer border using a mixture of a surfactant, a binding agent, and graphitic carbon powder. For example, one mixture can include isopropyl alcohol, nafion ionomer, and carbon black. A graphite electrode can avoid using a small diameter wire (which may be prone to breaking if subjected to repeated mechanical stress via the electrical contact) in the groove of the diagnostic spacer. A tab on the outside of the spacer may also be coated with the graphitic mixture to create a contact pad by which an electrical lead may be attached by mechanical fastener such as a lug or clamp. In some embodiments, a combination of a wire electrode and a graphite electrode can be used in the diagnostic spacer border. When a combination of a wire electrode and a graphite electrode are used, the wire can be placed in the groove such that a lead is disposed to the internal cavity of the spacer border. Next, the graphitic mixture can be injected around the wire electrode to fill the gaps in the groove and to coat the externally disposed tab. The tab extending from the external wall of the spacer border may be coated to supply an electrical contact for a voltmeter to attach. A doctor blade can be used to wipe away excess material and create a flat surface with the top of the spacer border. Such combination embodiments can alleviate concerns of breaking a thin wire electrode lead while also maintaining the ability to make good electrical contact with the internally disposed surface of the spacer border.
In step 503, a filler material such as a curable polymer solution can be applied to the groove containing the embedded electrode in the spacer border. The filler material can fill the voids between the spacer border and the embedded electrode in the groove.
If the filler material is a curable polymer solution, the curable polymer solution is cured in step 504.
In step 505, a wire lead can be connected to the embedded electrode. This connection can be connected by a solder joint 6 formed by a soldering device 12 as shown in
In step 506, an electrochemical device can be assembled. A membrane stack can include one or many diagnostic spacer borders placed regularly throughout the membrane stack. For example,
After assembly and during operation, the voltage drop across the diagnostic spacers placed at regular intervals can be monitored to verify expected performance and monitor trends. The initial assembly may result in irregularities in performance due to improper lay up of membranes. However, these anomalies can be readily identified using the in situ voltage drop monitoring. The defective region can be identified and removed, where previously the entire stack would have had to be entirely reassembled. During operation of the electrochemical device, trends in the voltage drop data can allow early identification of regions of the device that may be being affected by scale formation and/or blockage. As such, an operator can provide corrective maintenance more readily than in the previous designs described in the Background of this application.
In larger membrane assemblies, it may be advantageous to have many of the voltage leads. The signals from these leads can be collected to be reported to an operator. A multiplexer may be used to collect the large number of signals to be processed by a programmable logic controller (PLC) or data acquisition device. The PLC may also determine which diagnostic electrodes are in contact with what brine chambers. The brine chambers typically have a much greater conductivity than a dilute chamber and can provide superior precision for the voltage drop measurement in the cell.
In some embodiments, multiple electrodes can be placed and embedded along the perimeter of the interior cavity of the spacer border. This can allow for more detailed monitoring of the internal characteristics of the system within a given layer. For example, the location of a potential blockage may be more accurately identified. In addition, the mapping of the internal flow patterns within a layer and irregularities in the rate of salt removal may also be accomplished. Furthermore, problems with the electrodes can be identified if a region along the membrane does not appear to be operating properly, i.e., removing salt.
In addition to voltage drop monitoring, proper compression can be essential for maintaining membrane assembly performance. Internal and external leaks can result in parasitic performance losses and can potentially lead to hazardous conditions for operators. Active monitoring of compression can be accomplished with a strain gauge mounted to the compression plates used to hold the membrane assembly together.
In step 701, the position of the inlet and/or outlet ports are located with respect to the compression plate.
In some embodiments, there may be more than two inlet or outlet ports. As such, the position can be at a point near the center of the compression plate between or just below the center most ports. In such embodiments, when the strain gauge is affixed to the compression at such a position, the strain gauge can measure the change in deflection and still serve the same purpose as in the case of which one pair of inlet or outlet ports. The central location can be important as this position on the compression plate can see the greatest amount of deflection compared to the uncompressed state.
This position is where the strain gauge(s) will be affixed on the external side of the compression plate opposite the membranes. Placing the strain gauge or gauges in this location can provide the most accurate indication of changes that may affect the internal sealing of the assembly. In some embodiments, the strain gauge(s) can be placed far away from bolts or edges of the compression plate such that deflection will result in a more pronounced signal.
Before the strain gauge(s) can be added to the compression plates, the compression plates should be cleaned of all debris (step 702).
In step 1101, the voltage signal from the strain gauge can be input to a PLC. Changes to the amount of compression over time can be monitored by the PLC. In step 1102, the PLC can display values on HMI. At step 1103, the various measured voltage signals can be compared to threshold limit for voltage signal. If the measured voltage signals fall below the threshold voltage signals, an operator can be alerted. At step 1104, an operator can inspect the device in the areas alerted to him by the PLC and can then perform required maintenance if necessary to retighten the compression system such as tightening the bolts between compression plates. In step 1105, the operator can then check the strain gauges after performing the maintenance to make sure that the strain is now within the threshold boundaries and then the process can pick back up again at step 1102. During the maintenance operation, the output from a strain gauge can indicate when adequate compression is reapplied. Preventative maintenance of this type can prevent loss of performance or damage to cell components. As such, the system can aid in original assembly by providing feedback in the manufacturing process to guarantee adequate compression prior to commissioning.
In some embodiments, the compression can be monitored via measurement of distance between the compression plates. For example, a light source can be reflected off of the opposite compression plate and then captured by a sensor on the device. The time between generating the light signal and capturing the returned light can be converted into the distance between two points. By measuring the distance at multiple locations around the perimeter of the electrochemical ion separation device's compression plates, the uniformity of the compression can be monitored. A lack of uniformity in compression can lead to poor flow distribution and thus poor performance.
DefinitionsUnless defined otherwise, all terms of art, notations and other technical and scientific terms or terminology used herein are intended to have the same meaning as is commonly understood by one of ordinary skill in the art to which the claimed subject matter pertains. In some cases, terms with commonly understood meanings are defined herein for clarity and/or for ready reference, and the inclusion of such definitions herein should not necessarily be construed to represent a substantial difference over what is generally understood in the art.
Reference to “about” a value or parameter herein includes (and describes) variations that are directed to that value or parameter per se. For example, description referring to “about X” includes description of “X”. In addition, reference to phrases “less than”, “greater than”, “at most”, “at least”, “less than or equal to”, “greater than or equal to”, or other similar phrases followed by a string of values or parameters is meant to apply the phrase to each value or parameter in the string of values or parameters. For example, the spacing between ion exchange membranes can be less than about 1000 microns, about 500 microns, or about 250 microns is meant to mean that the spacing between ion exchange membranes can be less than about 1000 microns, less than about 500 microns, or less than about 250 microns.
As used herein, the singular forms “a,” “an,” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise. It is also to be understood that the term “and/or” as used herein refers to and encompasses any and all possible combinations of one or more of the associated listed items. It is further to be understood that the terms “includes, “including,” “comprises,” and/or “comprising,” when used herein, specify the presence of stated features, integers, steps, operations, elements, components, and/or units but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, units, and/or groups thereof.
This application discloses several numerical ranges in the text and figures. The numerical ranges disclosed inherently support any range or value within the disclosed numerical ranges, including the endpoints, even though a precise range limitation is not stated verbatim in the specification because this disclosure can be practiced throughout the disclosed numerical ranges.
The above description is presented to enable a person skilled in the art to make and use the disclosure, and is provided in the context of a particular application and its requirements. Various modifications to the preferred embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments and applications without departing from the spirit and scope of the disclosure. Thus, this disclosure is not intended to be limited to the embodiments shown, but is to be accorded the widest scope consistent with the principles and features disclosed herein.
Claims
1. An ion-exchange device comprising:
- a pair of compression plates, wherein at least one of the compression plates comprises a strain gauge on an outer surface of the at least one compression plate;
- a pair of electrodes comprising an anode and a cathode between the pair of compression plates;
- a first ion exchange membrane and a second ion exchange membrane between the pair of electrodes, wherein the first ion exchange membrane comprise at least two inlet or outlet ports,
- wherein the strain gauge is located at a position on the outer surface of the at least one compression plate corresponding to a point between the at least two inlet or outlet ports of the first ion exchange membrane.
2. The device of claim 1, wherein the first ion exchange membrane is a cation exchange membrane and the second ion exchange membrane is an anion exchange membrane.
3. The device of claim 1, wherein the position of the strain gauge on the outer surface of the at least one compression plate is equidistant between the at least two inlet or outlet ports of the first ion exchange membrane.
4. The device of claim 1, wherein the strain gauge is connected to a data acquisition device.
5. The device of claim 1, wherein the strain gauge is attached to the outer surface of at least one compression plate via adhesive.
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Type: Grant
Filed: May 23, 2023
Date of Patent: Jun 4, 2024
Patent Publication Number: 20230285902
Inventors: Michael James Connor, Jr. (Porter, TX), Brian M. McDonald (Austin, TX), Ethan Demeter (The Woodlands, TX), Thomas Beales (Houston, TX)
Primary Examiner: Anthony R Shumate
Application Number: 18/321,887
International Classification: B01D 53/22 (20060101); B01D 61/48 (20060101); B01D 61/52 (20060101); B01D 63/08 (20060101);